Process for the manufacture of condensation products containing phosphorus, the products and their use as flameproofing agents

ABSTRACT

The subject of the invention is a process for the manufacture of condensation products of hydroxymethyl-phosphonium compounds and a cyclic urea, characterized in that (a) 1 mol of a tetrakis(hydroxymethyl)-phosphonium compound is condensed at 40* to 120*C with (b) 0.02 to 0.5 mol, preferably 0.1 to 0.3 mol, of an optionally N-methylolated monocyclic or bicyclic urea, which has 5 to 6 members per ring, optionally in the presence of formaldehyde or a formaldehyde-releasing agent and optionally in the presence of an inert organic solvent, if appropriate, condensation is thereafter continued at 100* to 150*C and if appropriate free hydroxyl groups are at least partially etherified with at least one alkanol with 1 to 4 carbon atoms and if appropriate the salts of the polycondensation products are converted into the corresponding hydroxides. The condensation products are used for flameproofing organic fibre material, in particular textiles.

United States Patent l i Nachbur et a]- l l Aug. 26, 1975 {75]Inventors: Hermann Nachbur, Dornach;

Arthur Maeder. Thcrwil. both of Switzerland [73] Assignee: Ciba-GeigyAG, Basel. Switzerland [22] Filed: Aug. 31, I972 [21] Appl. No: 285,174

[30] Foreign Application Priority Data Sept. I0. I971 Switzerlandllllllllllllllllllll l33U8/7l Jan. I4, I972 Switzerland o. |7/72 {52}US. 427/390; 260/] P; 260/3091; 260/6065 P [51] Int. Cl C09d l/OO Fieldof Search Il7/l36, 138,8 F. 139.5 A ll7/l43 A; 260/3097, 606.5 P, ZSI P[56] References Cited UNITED STATES PATENTS lhllBH-ll Ill/I957 Reeves etal 160B 3.} IUAZU 3/l)(17 Wt'igncrH r H. 1173612 3.421.923 H1969 (juth Il7ll 36 X T AZSAXU Z/Wh) Wagncr et ul. I l'i/Uh 3.669.715 6/1972 Nachharet ul lI7/l3fi $681124 8/1972 Selloet ul. r v l. 117/136 3.690941 Reutcret al 4. I l7/l 36 FOREIGN PATENTS OR APPLICATIONS 884.785 I2/I96lUnited Kingdom Primary ExaminerMichael R. Lusignan Almmzy, Agenl, 0rFirm-Joseph G. Kolodny; Prahodh I. Almaula; Edward McC. Roberts I 57ABSTRACT The subject of the invention is a process for the manufactureof condensation products of hydroxymethylphosphonium compounds and acyclic urea. charac terized in that (a) l mol of atetrakis-(hydroxymethyl)-phosphonium compound is condensed at to 120Cwith (b) 0.02 to 0.5 mol, preferably O.l to 0.3 mol, of an optionallyN-methylolatcd monocyclic or bicyclic urea. which has 5 to 6 members perring, optionally in the presence of formaldehyde or aformaldehyde-releasing agent and optionally in the presence of an inertorganic solvent. if appropriate. con densation is thereafter continuedat I00 to C and if appropriate free hydroxyl groups are at leastpartially etherified with at least one alkanol with I to 4 carbon atomsand if appropriate the salts of the polycondensation products areconverted into the corresponding hydroxides The condensation productsare used for flameproofing organic fibre material, in particulartextiles.

14 Claims, N0 Drawings PROCESS FOR 'l'Hl'I ZHANL'FAUTURE ()FCONDENSATION PRODUCTS CONTAINING PHOSPHORL'S. THE PRODUCTS AND THEIRLFSE AS FLAMICPROOFING AGENTS The subject of the invention is a processfor the manufacture of condensation products of hydroxymethylphosphonium compounds and a cyclic urea. characterised in that (a)I mol of a tetrakis-thydroxymethyllphosphonium compound is condensed to40 to l2l)( with lb) 0.0] to 0.5 mol. preferably 1).] to (L3 mol. of anoptionally N methylolated monocyelic or bicyclic urea. which has 5 to 1members per ring. optionally in the presence of formaldehyde or aformaldehydereleasing agent and optionally in the presence of an inertorganic solvent. if appropriate. condensation is thereafter continued atlUll to l5llC and if appropriate free hydroxyl groups are at leastpartially etherified with at least one alkanol with l to 4 carbon atomsand if appropriate the salts of the polycondensation products areconverted into the corresponding hydroxides.

lhe condensation is preferably carried out at 70 to I C in an inertorganic solvent or solvent mixture. For this aromatic hydrocarbons areabove all suitable. such as. for example. toluene. o. mor p-xylene or ami\ture thereof. or \ylene-toluene. xylene-benzene or\ylene-decahydronaphthalene mixtures. Preferably the furthercondensation which may follo subsequently is carried out at l to l4t)(or especially at about l35('. that is to say at the boiling point of thesolvent or solvent mixture.

At the same time it is however also possible to carry out thecondensation in the absence of an inert organic solvent. for example ifcondensation product already manufactured is used as the solvent or ifcondensation is carried out in the melt.

An appropriate procedure is to heat the tetrakis- (hydroxymethyl)-phosphonium compound. which as a rule is in the form of an aqueoussolution. together with the component lb). optionally in a solvent. tothe boil. and to distil off the water.

'lhe tetrakis-thydroxymethyll-phosphonium compounds are. above all. thesalts and the hydroxide.

Suitable tetralyis-( hydrovy methyl )-phosphonium salts are. forexample. the formate. acetate. phosphate or sulphate and the halides.such as. for example. the bromide especially the chloride.'letrakislhydroxymethyll-phosphonium chloride is hereafter referred toas 'l HIL'.

Where tetrakis-t hydroxymethyl)-phosphonium hy droxide ITHPUH) is usedas the starting product. it is appropriately prepared beforehand from acorresponding salt. for emmplc 'l HPC. by neutralisation in aqueoussolution. preferably at a pH value of 7 to 7.5. with a base. fore\aniplc sodium hydnnide. and subsequent dehydration.

Suitable cyclic urcas correspond for example to the optionallymethylolated compounds of the formula wherein A denotes an alkyleneradical with 2 or 3 carbon atoms in the chain. optionally substituted byby droxyl. lower alkyl. lower alkoxy or lower alkoxyalkoxy. or wherein Adenotes a lower N-alkylamino-N.N- dimethylene radical or a4.5-ethyleneurea radical.

Lower alkyl and alkoxy usually contain at the most 4 carbon atoms. forexample methyl. ethyl. isopropyl. n-butyl. methoxy. ethoxy. n-propoxy ortert. butoxy. Appropriately. lower alkoxyalkoxy contains at most 4carbon atoms in each of the two alkosy radicals.

These cyclic ureas are preferably optionally N- methoylolated compoundsof the formula wherein A represents a radical of the formula wherein Xdenotes hydrogen. alkyl with l to 4 carbon atoms. hydroxyalkyl with 2 to4 carbon atoms or alkoxyalkyl with l to 4 carbon atoms in the alkoxypart and 2 to 4 carbon atoms in the alkyl part. Y and Z each denotealkyl with l to 4 carbon atoms. and R denotes alkyl or hydroxyalkyl withl to 4 carbon atoms.

The component (b) can thus be used in the N- methylolated ornon-methylolated form. Simple cyclic ureas. such as the ethyleneurea.propyleneurea or acetylenediurea. are preferably employed in thenonmethylolated form. On the other hand. substituted ureas. such as. forexample. glyoxalurea. 4-methoxy- 5.5-dimethylhexahydropyrimidoneQ or N-ethyltriazone. are preferably used in the form of their mcthylolcompounds. that is to say preferably in the form of N.N'-dimethylolcompounds.

The N-alkyltriazones correspond. for example. to the formula t l Iwherein R denotes alkyl or hydrosyalkyl with l to 4 carbon atoms.Preferably. R in the formulae (2.5) and (3) represents ethyl.

'lhe hexahydrtipyrimidones correspond preferably to the formula whereinX. Y and 7. have the indicated meaning. Preferably, however. X. Y and 7.in formulae (2.4) and [4) each denotes a methyl radical.

Amongst the cyclic ureas. ethyleneurea is especially preferred.

Where formaldehyde is optionally used conjointly it is preferablypresent as an aqueous solution. Paraformaldehyde is particularlysuitable as a formaldehydereleasing agent.

Where a condensation product. which still contains free hydroxyl groups.is optionally etherified. this is carried out for example withn-butanol. n-propanol. ethanol or especially methanol. This ispreferably carried out in an acid medium.

The acid catalysts optionally used conjointly in the condensation arepreferably salts which have an acid action (Lewis acids). such asmagnesium chloride. iron-Ill chloride. zinc nitrate or borontril'luoride/- diethyl ether. The conjoint use of these catalysts isespecially advisable in the autocondcnsation of THPOH.

After completion of the condensation and the optional etherilication,the salts of the condensation products can also be completely orpartially converted into their corresponding hydroxides. which is as arule cffected by adding strong bases such as alkali metal hydroxides oralkaline earth metal hydroxides. for example sodium hydroxide, potassiumhydroxide or calcium hydroxide. or also sodium carbonate. The amount ofbase is appropriately so chosen that the pH value of the reactionmixture is about 5 to 8. Appro riately. this conversion is carried outin the bath used for application.

At times. the end products show an unpleasant odour caused by volatile;low molecular trivalent phosphorus compounds, for example phosphines.such as trihydroxymethylphosphine. 'lhis odour can be eliminated by anoxidutivc after-treatment of the condensation product. for example bypassing air or oxygen into the reaction mixture or by adding oxidisingagents such as hydrogen peroxide or potassium pcrsulphate.

The condensation products are used for flamcprool ing organic fibrematerial. in particular textilesv For this, an appropriate procedure isto apply to these materials an aqueous preparation which contains atleast i a condensation product of the indicated type and 2) apolyfunctional compound which differs from the condensation productsaccording to l and to finish the materials treated in this way by themoist batch. wet batch. or above all the ammonia or. especially. thetherniofising process.

The component 2) is preferably a polylunctional cp oxide or above all apolyfunctional nitrogen compound. Possible cpoxidcs are above allepoxidcs which arc liquid at room temperature and have at least t\\ocpoxidc groups. which are preferably derived from polyhydric phenols.Polylunctional nitrogen compounds are. for example.polyalkylcnc-polyamines or cspccially coinill (ill

pounds which form aminoplasts. or aminoplast precondensates. The latterare preferred.

By compounds which form aminoplasts there are understood nitrogencompounds which are methylolated and by aminoplast precondensates thereare understood addition products of formaldehyde to nitrogen compoundswhich can be methylolated. As compounds which form aminoplasts or asnitrogen compounds which can be methylolated. there may he mentioned:

l.3.5-Aminotriazines such as N-substituted melaniines. for exampleN-butylmelamine. N- trihalogenomethylmelamines. triazones and ammeline.guanamines. for example benzoguanamines and acetoguanamines or alsodiguanamines.

Further possibilities are: eyanamide. acrylamide. an alkylurea or anarylurea and alkylthioureas or arylthioureas. alkyleneureas oralkylenediureas, for example. urea. thiourea. urones. triazones.cthyleneurea. propyleneurea. acetylenediurea or especially4.5-dihydroxyirnidazolidone-2 and derivatives thereof. for example4.S-dihydroxyimidazolidone-2 substituted in the 4-position. at thehydroxyl group. by the radical -CH- C"H- ,CONHCH. ,OH. 'l'he methylolcompounds of a urea. of an ethyleneurea or. especially. of melamine arepreferentially used. Valuable products are in general given by productswhich are as highly methylolated as possible but in particular also byproducts with low methylolation. Ethcril'icd or non-etherifiedmethylolmelamines are particularly suit-able. such as dimethylolmclamincor trimethylolmelaminc or mixtures thereof. Suitable aminoplastprccondensatcs are both predominantly monomolecular aminoplasts and alsomore highly precondenscd aminoplasts.

The ethers of these aminoplast prccondcnsates can also be used togetherwith the reaction products. For example. the cthcrs of alkanols such asmethanol. ethanol. n-propanol isopropanol. n-butanol or pentanols arcadvantageous. It is. however. desirable that these aminoplastprccondensates should be watensoluble. such as. for example,pentamcthylolmelamine dimcthyl-cther ortrimcthylolmclamine-dimethyl-ethcr.

The organic fibre materials which are to be provided with a flameprooffinish are. for example. wool. paper, furs. hides or preferablytextiles. In particular fibre materials of poly-amides. cellulose.cellulose-polyester or polyester are rendered flamcproof in which casefabrics of wool. polyester or especially mixed fabrics ofpolycstor-cellulose. wherein the ratio of the polyester constituent tothe cellulose constituent is l:4 to 2:] are preferred. It is thuspossible to use. for example. so-called 20/8". 26/74. 50/50 or (17/33polyester-cellulose mixed fabrics.

The cellulose or the cellulose constituent of the fibre materialoriginates. for example. from linen. cotton, rayon or staple viscose. inaddition to polyestercellulose fibre mixtures. fibre mixturesolccllulose with natural or synthetic polyamidcs can also be used. Aboveall it is also possible to render librc materials of wool llamcproofsuccessfully with the polycondensa tion products.

The aqueous preparations for llamcprooling the organic fibre materialsas a rule contain ZUll to Xllll g/l. preferably 350 to 7(lll g/l.especially also 'lllll to 600 g/l. of the component i l J and Ill to 200g/l. preferably 40 to I21) g/l. of the component (I). l hc preparationsin most cases ha\c an acid to neutral or weakly alkaline pH value.

The preparations for flamcproofing can optionally contain yet furtheradditives. To achieve a greater deposit of substance on fabrics it isadvantageous. for example. to add (H to 0.5% of a high molecularpolyethylene glycol. Furthermore. the customary plasticisers can beadded to the preparations. for example an aqueous polyethylene emulsionor silicone oil emulsion.

To improve the mechanical strengths of the fibres it is also possible toadd to the preparations suitable copolymers. for example copolymers ofN- methylolacrylamide or also cationic copolymers. Advantageous for thispurpose are. for example. aqueous emulsions of copolymers of a) 0.25 topercent of an alkaline earth metal salt ofan a. B-cthylenicallyunsaturated monocarboxylic acid. b] 0.25 to 30 percent of aN-methylolamide or N-methylolamide-ether of an a. B-ethylenicallyunsaturated monocarboxylic or dicarboxylic acid and c) 99.5 to 60percent of at least one other copolymerisable compound.

These copolymers and their manufacture are known. The tear strength andabrasion resistance of the treated fibre material can be favourablyinfluenced by the conjoint use of such a copolymer.

If a polymer of the indicated type is also added to the preparation. itis advantageously added in small amounts. for example 1 to 10 percentrelative to the amount of the condensation product. The same is true ofany plasticiser. where the appropriate amounts can again be 1 to 10percent.

It is also possible to add curing catalysts. such as. for csample.ammonium chloride. ammonium dihydrogen orthophosphate. phosphoric acid.magnesium chloride or zinc nitrate. but is in most cases not necessary.

The pH value of the preparations is as a rule 2 to 7.5. preferably 4 to7. and is adjusted in the usual manner by adding acid or base.

it can also be advantageous to add buffer substances. for exampleNaHCTh. disodium and trisodium phosphate or triethanolaminc.

To improve the durability of the flameproof finishes and to achieve asoft handle it can be advantageous to add. to the aqueous preparations.halogenated paraffins in combination with a polyvinyl halide compound.

The preparations are now applied to the fibre materials. which can bedone in a manner which is in itself known. Preferably. piece goods areused. and these are impregnated on a padder which is fed with thepreparation at room temperature.

In the preferred thcrmofixing process. the fibre material impregnated inthis way must now be dried and subjccted to a heat treatment. Drying isappropriately carried out at temperatures of up to l00C. Thereafter thematerial is subjected to a heat treatment at temperatures aboye 100%.preferably 100 to 200C. preferably I" to lstl C. the duration of whichcan be the shorter the higher is the temperature. This duration ofheating is. for cumtple. seconds to 10 minutes.

it is. ho\\c\cr. also possible to use the ammonia fixing process ormoist fixing process or the wet fixing process.

If the moist fining process is used. the fabric is first dried to aresidual moisture of about 5 to 20 percent and is thereafter stored forII to 48 hours at about to C. rinsed. washed and dried. In the wetfixing pro cess a similar procedure is followed. except that thecompletely ct fibre material is stored. In the ammonia fixing process.the treated fibre material is first gastreated with ammonia whilst moistand is subsequently dried.

A rinse with an acid-binding agent. preferably with aqueous sodiumcarbonate solution. can be appropriate in the case of a strongly acidreaction medium.

In the examples which follow. the percentages and parts are percentagesby weight and parts by weight. respectively. The relationship of partsby volume to parts by weight is as of ml to g.

EXAMPLE 1 244 parts ofa 78 percent strength aqueous THPC solution lmol). 43 parts of ethyleneurea (0.5 mol) and 200 parts of xylene isomermixture are heated to the boil. with rapid stirring. in a stirred vesselof 500 parts by volume capacity. which is provided with a waterseparator and thermometer. At a boiling point of 102C. the azeotropicremoval of the water from the aqueous THPC solution commences. Afterthis water has been removed. the boiling point gradually rises to 134C.in the course of which further water. which has been formed bycondensation. is obtained. In total. 80 parts of water are obtained. Thereaction product forms a highly viscous mass and is cooled to 90C. afterwhich the product is dissolved by adding 200 parts of water. The xyleneis largely separated off and the aqueous solution is completelyevaporated in vacuo at about C.

200 parts of a yellow. highly viscous product are obtained and arediluted with water to 80 percent active substance content to facilitatehandling. The infrared spectrum of this product shows the followingbands:

Broad hand at appro\v 3.340 cm strong Sharp 2.900 eak Broad shoulder2.850 medium Broad shoulder 2.640 medium Broad shoulder 2.470 cal; Broadshoulder 2.350 weak Sharp 3.070 \rcakmedium llroad l.o7o strong SharpL490 medium strong Broad 1.440 weak Sharp shoulder l 390 weakmediumSharp shoulder L300 cakmedium Broad 1.265 \ycak Sharp L205 cak Broadl.|55 \\cak Sharp L095 weak Sharp l .1 I40 medium Broad H0 medium Sharp750 eak EXAMPLE 2 244 parts of a 78 percent strength aqueous solution ofTHPC ll mol) and 43 parts of cthyleneurea (0.5 mol) are treated for 2hours at I00 to l l0C internal temperature in a stirred vessel of 500parts by volume capacity. which is equipped with a thermometer andreflux condenser. After cooling to room temperature. a yellow. lowviscosity solution of the condensation product. containing percent ofactive substance. is obtained.

The infrared spectrum of this product shows the following bands:

Broad hand at approx. 3.300 cm strong Sharp 2.! l 0 calx Broad shoulder1.850 medium -(ontinued Broad shoulder 21130 medium Broad shoulder 2.460u ealt Broad shoulder 3.350 eal- Sharp 3.070 eak Broad 1.690 strongBroad shoulder I .640 medium Sharp 1.495 medium Broad 1.440 \teak Sharpshoulder 1.390 eakmedium Broad 1.370 medium Broad 1.305 \wak Sharp 1.105\sealt Sharp 1.040 medium strung Sharp shoulder 910 medium Broadshoulder X80 cal. Sharp 750 Ctlls EXAMPLE 3 244 parts of a 78 percentstrength aqueous solution of'I'HPC 1 mol of THPC) and 50 partsofpropylencurea (0.5 mol) are treated for 2 hours at 100C internaltemperature in a stirred vessel of 500 parts by volume capacity which isequipped with a thermometer and reflux condenser. 'I'hereafter themixture is cooled to room temperature and 293 parts of a clearcolourless solution containing 81.6 percent of active substance areobtained. The infrared spectrum of this product shows the followinghands:

Broad hand at approx. 1 240 em strong Sharp 3 I30 Ctlls Broad shoulder2.8 50 medium Broad shoulder 3 30 eukmedium Broad shoulder 2.470 \seakBroad shoulder 3.350 unis Sharp 3.030 eukmedium Broad 1.640 strong Broad1.535 medium Sharp shoulder 1.450 \\Ci|i\' medium Broad 1.410 L'itlvmedium Sharp l .3 30 weakmedmm Sharp 1.395 eukmedium Sharp 1. 15cakmedium Broad shoulder 1.190 \\eak Broad shoulder 1.1h5 \ieak Sharp1.110 \teak Broad 1.045 medium Sharp shoulder 050 cakmedium Sharpshoulder 9 l0 healtmedium Broad shoulder 8S0 eakmedium Sharp 750\scakmedium EXAMPLF. 4

244 parts of a 78 percent strength aqueous solution of 'lHPC 1 mol ofTHPC) and 355 parts (035 mol) of an acetylcncdiurea are treated for 2hours at 100C internal temperature in a stirred vessel of 500 parts byvolume capacity which is equipped with a thermometer and refluxcondenser. 279 parts ofa colourless low \'is cosit solution whichcontains 89.6 percent of active substance are obtained. The infraredspectrum of this product shows the following bands:

Hroad hand at appro\ 3.340 cm strong ('ontinucd Sharp 3. 10 Weak liroadshoulder 3.350 medlum Hroad shoulder 3.030 medium Hroud shoulder 3.470\xeak 5 Hroadshouldcr 3.350 weak Sharp 3.070 weakmedium liroad 1.670strong Broad shoulder 1.645 medium Broad 1.470 mediumstrong lU Broad1.410 cakmedium Sharp 1,3 eak Sharp shoulder 1.345 weak l'lroad shoulder1.310 neak Sharp 1.105 weak Sharp 1.040 medium- 15 strong Sharp shoulderH0 medium Broad shoulder H75 \-.eak

medium Broad shoulder 755 eak EXAMPLE 5 244 parts of a 78 percentstrength aqueous solution ofTHPC (1 mol ofTHPC) and 2325 parts [0.5moles) of a 40 percent strength aqueous solution of N.N'- 2Sdimethylol-glyoxalurea are treated for 2 hours at 100 to 105C internaltemperature in a stirred vessel of 500 parts by volume capacity which isequipped with a thermometer and reflux condenser. 'l'hercafter themixture is cooled to room temperature and 463 parts of a \cllow-red lowviscosit solution containing 56 percent of active substance areobtained. The infrared spectrum of this product shows the followingbands:

Broad hand at appro\ .350 cm strong i Shar 3.)10 neak Broad shoulder3.350 medium Broad shoulder 3.040 cal.-

medium liroad shoulder 3 350 weak Sharp 3 070 L'ills 4U liroad l 7|0strongmedium lhoad houlder l.h mediumneak Broad 1.470 medium Broad L310\teak Broad I .340 weak 5 Sharp 1.160 eak Sharp 1.040 medium Broad J00weal;-

medium Sharp shoulder 750 \seak EXAMPLF. a

244 parts of a 78% strength aqueous solution of 'IHPC 1 mol of'l'HPC)and 218 parts (0.5 mol) of a percent strength aqueous solution of N.Ndimeth lol-4-mcthot -5.5-dimeth lhexahydropyrimidone-3 are treated for 3hours at C internal tem perature in a stirred vessel of 500 parts byvolume capacity which is equipped with a thermometer and refluxcondenser. lhcreafter the mixture is cooled to room temperature and 460parts of a clear low viscosity solution containing (11.7 percent ofactive suhstance are obtained. lhc infrared spectrum of this productshows the following hands:

llroad hand at appnn .340 cm strong Sharp 3.010 \ieak Hroad shoulder3.960 medium Hroad houldei 3. 0 \walv -(ontinued medium Broad shoulder1,470 eak Hroad shoulder 1.350 eak Sharp ltl' tl \yeak liroad 11-50strong Broad l5! medmm \\L'ill\ Broad l .405 eak llroad shoulder L100eak liroad L245 eak Broad shoulder l.l 5 eak Sharp shoulder l.ll1 ealtBroad l.l r-lu weakmedium Broad )lll) weal-tmedium Sharp 755 eal;

E X A MPl .F. 7

Broad hand at appro\ 3,240 strong Broad shoulder I. cult Broad shoulder2 weak llroad shoulder I. cult llroad shoulder Z. \\eak llroad shoulder1.. heals Shar shoulder 1. weakmedium llroad shoulder L700 stroru.llroad shoulder 11:50 neak lllorul 1.540 cult llroatl shoulder L400 weakBroad shoulder I300 cal; liroad shoulder L145 weak l'lrorid shoulderLII! cal;

l'lroad L0 5 eak Broad N05 weak EXAMPLE I905 parts i 1 mol) of anhydrouscrystalline 'lHPC and I7] parts (0.02 mol) of ethyleneurea are condensedin the melt at l 15C for 2 hours. in a stirred vessel of 500 parts byvolume capacity which is equipped with a thermometer and relluxcondenser. 'l'herealter the mixture is cooled to 50C. 80 parts ofmethanol and 0.1 part of 37 percent strength aqueous hydrochloric acidare added and the mixture is etherilied for minutes at the rellu\temperature (05 661). I! is then cooled to (0C and the e\cess methanolis removed in \acuo. l) l parts ol'a viscous condensation product areohtained The infrared spectrum of this product shows the followinghands:

l'lroad hand .rl nppon .24 em strong Sharp Z5110 \setilt Broad houlder Ir\ lr earl.-

medium llr ad houlder 2.0 0 \ieals medium llroail shoulder -lhll \teakllroad shoulder I. -lrr \tcals Sharp 1,070 weak liroad 1.010 medium-Continued Broad shoulder L500 weak Broad 1.4 l 5 medium Sharp l .300weak Broad shoulder l .260 weak Broad L800 weak Sharp shoulder 1.165weak Broad shoulder l I00 weak Sharp l l)4(| mediunr strong Sharpshoulder I 5 medium Broad shoulder H \nealo medium EXAMPLE 9 244 partsof an aqueous 78 percent strength THPC solution l mol), 30 parts ofpropyleneurea (0.3 mol) and 5 l parts of an aqueous 35.4 percentstrength formaldehyde solution (0.6 mol) are condensed for 2 hours atl00 I05C internal temperature in a stirred vessel of 500 parts by volumecapacity which is equipped with a thermometer and reflux condenser.After cooling. 324 parts of a low viscosity clear solution of thecondensation product. containing 9.6 percent of phosphorus. areobtained. The infrared spectrum shows the following hands:

Broad hand at appro\. 3.240 cm strong Broad shoulder 2.) l 0 weak Broadshoulder lX-lll medium Broad shoulder 2.630 medium Broad shoulder 2.480weak Broad shoulder L350 weak Sharp 1070 medium Broad l.f |0 strongBroad 1.520 eakmedium liroad L405 \veakmedium Sharp shoulder L320ealsmedium Broad L395 eak Shar shoulder l.3 1 ll weak Broad shoulder llhll eak Sharp shoulder l |05 we; Broad l.0-l0 \sezllt" medium Broad J00cakmedium Shurp shoulder 750 \ieak EXAMPLE I0 244 parts of a 78 percentstrength aqueous solution ol- THPC l mol) are neutraliscd to a pH valueof 7.2 with 46.6 parts of 30 percent strength aqueous sodium hydroxidesolution in a stirred vessel of 500 parts by volume capacity which isequipped with a thermometer and reflux condenser. and thereafter 43parts of ethyleneurea (0.5 molt are added. Condensation is then carriedout for 2 hours at l00- l 10C internal temperature. 'lherealter themixture is cooled to room temperature.

320 parts ola mobile solution ol the condensation product, containing20.5 parts of NaCl. are ohtained. 'l'he phosphorus content is 9.7percent. The infrared spectrum ol this product shows the followinghands:

Br ad hand at approx 3,240 cm strong llroatl shoulder MIN) erds llroadshoulder 2.8 0 medium Broad shoulder 21-30 cakmedium Broad shoulder2.470 weak Broad shoulder 2.350 eak Sharp 1070 realtmedium EXAMPLE llThe procedure described in Example I is followed. 1 but only 2L5 partsof ethyleneurea (0.25 mol) are used. 65 parts of water are obtained fromthe azeotropic distillation. Yield: 2l7.5 parts (80 percent strengthaqueous solution). The P-content is l2.4 percent or product as such. Theinfrared spectrum shows the following bands:

follows. dried at H" to l00(' and subsequently cared for 5 minutes at150C.

The fabric is then washed for 5 minutes at (C in a liquor which perlitre contains 5 ml of hydrogen peroxide (35?! strength). 3 g of sodiumhydroxide solution (30% strength) and l g of a percent strength aqueoussolution of a condensation product of 1 mol of ptert.-nonylphenol and 9mols of ethylene oxide. Thereafter the fabric is rinsed and dried. Thedegree of fixing indicates the amount of the product present on thefibre material after rinsing (relative to the amount originallyabsorbed).

The fabrics are then washed up to 20 times for 45 minutes at (10C in adomestic washing machine. in a liquor which contains 4 g/l of a domesticdetergent (SNV l58.86l wash).

The individual fabric samples are then tested for their flameproofcharacter (DIN 53.906 vertical test; ignition time 6 seconds).

The results are summarised in Table l which follows.

Table l Constituents. g/l Untreated Treated with Liquor Productaccording to Example I 485 Product according to Example 2 520Dimethylolmelamine 96.5 96,5 pH value of the liquor 5.5 5.5 (adjustedwith NaOH) Liquor uptake ('Z) 75 75 Degree of fixing (Z l 82 87Flameproof character Smouldering time/Tear length (seconds) (cm) Afterrinsing burns 0/9 0/! 1.5 After 20 washes (60C) burns 6/61) Broad handat approx. i 240 cm strong EXAMPl .F. l 3 Sharp 3.)ll) weak Simum" J 'E40 Mixed fabrics of polyester-cotton (PBS/CO). 50:50

0 u t Broad shoulder loll) and 67:33. are padded with the liquorsaccording to Table 2 which follows. dried for minutes at 80C and liroadshoulder 2 Jon weak g q a mud \hnumcr 3 wk subsequently cured lorminutes at l 0 C. l 3 070 weak The fabric is then washed for 5 minutesat 60C in 11 Broad L685 medium 4 l. h. h I. I S l .h i Hnmd mum L045"mum" iquor w IC per ltrt. contains rn ol yc rogcii perox- Sherl1 1.4medium idc (35% strength). 3 g of aqueous sodium hydroxide Broadshoulder l -l-lll \teak- 1 t medium holutmn h l l 8 pert-L1H liroadshoulder L415 \tcak strength aqueous solution oi a condensation productol 7 q V rtlj l mol ol p-tert-nonylphenol and 9 mols of ethyleneoxlirmrd shoulder L200 gala ide. 'lhcreaftcr the fabric is rinsed anddried. The de- SI a Q ""T gree of fixing indicates the amount of productpresent Ill! Cit V y 5 wk on the fibre material after rinsing (relativeto the Sharp LlMI cult amount originally taken up). (I i r A i l "f 'ilhc labrics are then washed up to 40 times for bhaip ll lllt er Jltliiicdiuni o I liroad shoulder sso eat minutes at on C at a domesticwashing machine. in a limad liliilltlci' liL uor which contains 4 i of tdomestic dct r nt hhm'l H cak l EJ i L EXAMPLE I:

Mixed fabrics of polyester/cotton l PPS/('0) ((17/33) arc padded Withthe liquors according to Table l which (10 [SNV IQXXM wash). Theindividual fabric samples are then tested for their flanicproofcharacter (DIN 53.906 vertical test; ignition time (1 seconds).

The results are summarised in 'l'ablc 2 which follows.

Table 2 Constituents, g/l Untreated Treated with Liquor SIS Table 2-Continued Constituents. g/l Untreated Treated with Liquor C D E FProduct according to Example 7 650 Dimcthylulmeluminc 96.5 96.5 96.596.5 96.5 pH value of the liquor 5.3 5.5 5.4 5.4 5.8 (adjusted withNuOH) Fabrics. PES CO 50:50 67:33 50:50 67:3) 50:50 67:33 50:50 67:3350:50 67:33 50:50 67:33

Liquor uptake. '16 75 75 75 75 75 75 75 75 75 75 Degree of l'ixingfii 7i73 73 7| oil 71 68 78 75 78 Flumegrool' character After rinsingsmouldering time (seconds) burns 0 0 l 0 0 0 (I 0 0 0 tear length (cm) 9l0 9.5 I0 H M5 9.5 l3 ll After washes (60C) smouldering time (seconds)burns 0 2.5 0 0 0 0 0 0 0 0 tear length(cm) 7.5 9 9 I05 95 95 8 I3 95IL!) After 40 washes (60C) smouldering time (seconds) burns 0 0 0 2 0 I0 0 0 tear length (cm) 6.5 ll ll 9 9.5 U5 8 B 9 The phosphorus contentper kg of fabric is in each case 52 g.

EXAMPLE 14 as monia for 10 minutes. then treated for l0 minutes in abath which contains 300 ml of a 24 percent Fabrics ot' polyester/cotton(PES/CO) 67:33 and 50:50. 'ool (W) and cotton (C0) are padded with theliquors of Table 3 and 4 below and then after-treated as follows:

a. B the thermolixing process. with subsequent washing at 40C (W) (10C(PES/CO) or 95C (CO) as indicated in Example 12.

b. Partly b the ammonia fixing process: after padding. the fabrics aredried incompletely at 80C |0-20(' residual moisture). then gassed withamonds). Untreated fabrics burn away.

strength aqueous ammonia solution per litre. using a liquor ratio of[:30. thereafter rinsed at C in a bath which contains 5 g/l of soap and6 ml/l of hydrogen peroxide (35% strength). and dried.

The fabrics are then washed up to 20 times at 40C (W) or C (PES/CO) or95C (CO) as indicated in Example 12. and then tested for theirflameproof character according to DIN 53.906 (ignition time 6 sec- Theresults are summarised in Table 3 and 4 below.

Table 3 Constituents. g/l Treated and fixed according to process a)PES/CO 67:33 CO W H l J K L M N O P O R Products according to Example505 505 270 270 9 845 845 453 453 I0 840 690 l l 463Di-trimethylolmclamine I03 I03 I03 I03 96.5 I20 I20 I20 845Trimethylolmclaminedimethyl-ethert75'i strength) I53 I79 Condensationproduct" 2 Silicone oil emulsion 35 35 35 35 35 35 35 35 35 35 (40%strength) H l J K L M N O P O R pH of the liquor 5.5 5.5 4.5 7 7 5.5 5.55.5 4.5 7 7 Degree of fixingv it 57 52 67 77 SI 60 SI 63 69 96Flamcprool character: Burning time (seconds-)Itcar length (cm) AfterI'IY'lMflg 4H3 (1/8 ()lt'i (]/l I [)III ()/l l W6 (V5.5 016.5 (1/6 (1/4After I wash 3/12 0/I0.5 0/9 0/7 0/7 0/9 0/I0 0/6 0/5 (1/4 Aft 5 w h s3.5/10 0/I0 0/7 0/7.5 ()lli ()/9 ()/8 0/55 0/4 0/5 0/4 Alter 20 washes3/l I 0/ll 0/7 017.5 0/5 0/8 5* (I/K 0/7 0/4 0/5.5 0/3Hl'lLlKI'IVttllUfl producl of l moi of [t-lert -nun \lphenol and 9 mol\of ethylene mute l-lamcproofing test carried out after rinsing and after20 and 40 washes Table 4 ('onstituent. g/l 'l reated and I'ned accordingto process l b Pli h7g (O S T l Product according to Esample X 505 50*170 I70 Di-trinicth lolmela- I20 I30 mine Trimethylolmelaniinel5 l5?-dimethyl-ethcr I75"; strength! Silicone oil cmul- 35 5 35 35 sion (40%pH of the bath 5.5 5 F 5.5 5. g of phosphnrusf 57 7 35 kg of fabric g ofnitrogen! 30 30 40 40 kg of fabric Flamepruof character: burning timclseconds l/tcar length (cnn After rinsing (V0.5 /l I 0/7 0/5 After l h"/9 0/) 0/4 0/55 After washes u ss u/u (1/0 (If-L5 After 20 ashes tI/X(VH5 (1/0 0/7 EXAMPLE A fabric of pure polyester is padded with thefollowing liquor:

825 g/l of product according to Example I0 I g/l ofdi-trimethylolmelaminc g/l of silicone oil emulsion strength) pH value:7

Degree of fixing: 79%

After padding. the fabric is dried at 80 to C and thereaftercondensation is carried out for 5 minutes at 150C. The fabric is thenwashed for 5 minutes at 40C in a bath which contains 4 g/l of sodiumcarbonate and 1 g/l of a condensation product of l mol of p-tert.-nonylphcnol and J mols of ethylene oxide. rinsed and dried.

The flameprooling test according to DIN 5390b (ignition time 6 seconds)gives the following values:

2 seconds I 3.5 cm

Burning time lear length:

wherein X denotes hydrogen. alkyl with l to 4 carbon atoms.

liydroxyalkyl with 2 to 4 carbon atoms or alkoxyalkyl with l to 4 carbonatoms in the alkoxy part and 2 to 4 carbon atoms in the alkyl part, Yand Z each denote alkyl with l to 4 carbon atoms and R denotes alkyl orhydroxyalkyl with 1 to 4 carbon atoms; and [2) a polyfunctionalaminoplast precondensate. and curing the treated material by heating thetreated material for about 30 seconds to about 10 minutes. at atemperature in the range of about [00C to 200C after a drying step.

2. The process of claim I, wherein the water-soluble condensationproduct is obtained by condensing a tetrakis-( hydroxymethyl)-phosphonium salt. ethyleneurea. and methylolmelamine.

3. The process of claim I, wherein the condensation product is obtainedby condensing a tetrakis- (hydroxymethyl )-phophoniuni salt or hydroxidewith a cyclic urea in the presence of an inert organic solvent.

4. The process of claim 1, wherein the molar equivalent of the cyclicurea is in the range of0.l to 0.3.

5. The process of claim I. wherein the tetrakis- (hydroxymcthyl)-phosphonium salt is a tctrakis- (hydroxymethyl l-phosphonium halide.

6. The process of claim 1. wherein the cyclic urea is methylolatedbefore the condensation.

X denotes hydrogen. alkyl with l to 4 carbon atoms.

hydrosyalkyl with 2 to 4 carbon atoms or alkoxyalkyl with l to 4 carbonatoms in the alkoxy part and 2 to 4 carbon atoms in the alkyl part. Yand Z each denote alkyl with l to 4 carbon atoms and R denotes alkyl orhydroxyalkyl with l to 4 carbon atoms.

8. The process of claim I, wherein the cyclic urea is ethyleneurea.

9. The process of claim l, wherein the cyclic urea isN.N'-dimethylolglyosalurea.

[0. The process of claim I. wherein the condensation is carried out inthe presence of formaldehyde.

l l. The process of claim I. wherein the condensation product is atleast partially etherificd with an alkanol of l to 4 carbon atoms.

[2. The process ol'claim I, wherein the condensation product is obtainedby further condensation at a temperature of l00 to [50C.

IS. The process of claim 3, wherein the inert organic solvent includesan aromatic hydrocarbon.

[4. Organic l'ibcr material of a blend of polyesterccllulose which hasbeen provided with a flamcproofing linish by a process comprising thesequential steps of treating the material with an aqueous preparationwhich consists essentially of l l a water-soluble condensation productobtained by condensing a tetrakis (hydrox methyl tphosphonium salt orhydroxide at 40 to C with 0.02 to 0.5 molar equivalent of a cyclic ureaof the formula:

kyl with i tn 4 carhun atoms in the ulkuxy part and 2 to 4 curhun atomsin the alkyl purt. Y and 2 each tlcnntu ulkyi with l tn 4 carbon atomsand R dcnotcs alkyl ur hydroxyulkyl with i to 4 curhun atoms; and (2) npulyt'unctiunul uminnplust precundcnsnte. and curing the treatedmaterial by heating the treated material for about 30 seconds to a nutH) minutes at a temper'iture in the ran 'c 0! about 100C to 200C after adrying step. 5

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NO. 1 3,901,985 DATED August 26, 1975 |NVENTOR(S) I HERD ANNNACHBUR ET AL It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column 15, claim 1, line 66, delete "N- H" and substitute NH l Column16, claim 3, line 18, delete "phophonium" and substitute phosphoniumColumn 16, claim 7, line 30, delete "-CH-NH-CO-NHCH-" and substituteColumn 17, claim l t, lines t and. 5, delete "-CH-NH-CO-NH-CH" andsubstitute Etigncd and Scaled this twenLv-seventh D3) Of April 1976[SEAL] A nest:

RUTH C. MASON C. MARSHALL DANN 8 ffi ('mnmissinncr ujlure'nts andTrudemurkx

1. A PROCESS FOR FLAMEPROOFING ORGANIC FIBER MATERIAL OF A BLEND OFPOLYESTER-CELLULOSE, COMPRISING THE SEQUENTIAL STEPS OF TREATING THEMATERIAL WITH AN AQUOUS PREPARATION WHICH CONSISTS ESSENTIALLY OF (1) AWATER-SOLUBLE CONDENSATION PRODUCT OBTAINED BY CONDENSING ATETRAKIS-(HYDROXYMETHYL)-PHOSPHONIUM SALT OR HYDROXIDE AT 40 TO 120*CWITH 0.02 TO 0.5 MOLAR EQUIVALENT OF A CYCLIC UREA OF THE FORMULA: 2.The process of claim 1, wherein the water-soluble condensation productis obtained by condensing a tetrakis-(hydroxymethyl)-phosphonium salt,ethyleneurea, and methylolmelamine.
 3. The process of claim 1, whereinthe condensation product is obtained by condensing atetrakis-(hydroxymethyl)-phophonium salt or hydroxide with a cyclic ureain the presence of an inert organic solvent.
 4. The process of claim 1,wherein the molar equivalent of the cyclic urea is in the range of 0.1to 0.3.
 5. The process of claim 1, wherein thetetrakis-(hydroxymethyl)-phosphonium salt is atetrakis-(hydroxymethyl)-phosphonium halide.
 6. The process of claim 1,wherein the cyclic urea is methylolated before the condensation.
 7. Theprocess of claim 1, wherein A is a radical of the formula -CH2CH2-,-CH2CH2CH2-, -CHOH-CHOH-, -CHOX-CYZ-CH2, -CH2-NR-CH2-or-CH-NH-CO-NH-CH-wherein X denotes hydrogen, alkyl with 1 to 4 carbonatoms, hydroxyAlkyl with 2 to 4 carbon atoms or alkoxyalkyl with 1 to 4carbon atoms in the alkoxy part and 2 to 4 carbon atoms in the alkylpart, Y and Z each denote alkyl with 1 to 4 carbon atoms and R denotesalkyl or hydroxyalkyl with 1 to 4 carbon atoms.
 8. The process of claim1, wherein the cyclic urea is ethyleneurea.
 9. The process of claim 1,wherein the cyclic urea is N,N''-dimethylolglyoxalurea.
 10. The processof claim 1, wherein the condensation is carried out in the presence offormaldehyde.
 11. The process of claim 1, wherein the condensationproduct is at least partially etherified with an alkanol of 1 to 4carbon atoms.
 12. The process of claim 1, wherein the condensationproduct is obtained by further condensation at a temperature of 100* to150*C.
 13. The process of claim 3, wherein the inert organic solventincludes an aromatic hydrocarbon.
 14. Organic fiber material of a blendof polyester-cellulose which has been provided with a flameproofingfinish by a process comprising the sequential steps of treating thematerial with an aqueous preparation which consists essentially of (1) awater-soluble condensation product obtained by condensing atetrakis-(hydroxymethyl)-phosphonium salt or hydroxide at 40* to 120*Cwith 0.02 to 0.5 molar equivalent of a cyclic urea of the formula: